Interpolymers of acrylamides and allyl aceto-acetates and process of producing same



Patentcd Aug. 30, 1949 PQLRS F ACRYLAMIDES AND YE. AETO-ACETATES AND PROCESS GK" PRGBUCNG SAME Glmn it. tones, Eastern, a, assignor to General Aniline a Film Corporation, New York, N. Y., a corporation oi Delaware No wing. Application May 2, 1947,

r1 No. naeso This invention relates to novel interpolymers of amides oi B-ethylenically unsaturated monocarboxylic acids with a fin-ethylenically unset-=- urated lower aliphatic alcohol ester of acetoaeetic acid.

I have found that by interpolymerizing a mix-= ture of an amide of an a,p-ethylenically unsaturated monocarboxyiic acid with a finr-ethylenically unsaturated lower aliphatic alcohol ester of acetoacetic acid in the manner customary in forming interpolymers of vinyl compounds, it is possible to produce novel water-soluble interpolymers which yield clear viscous solutions and which are quite useful in the art.

The details oi the present invention will be apparent from a consideration of the following specific example of a preferred embodiment thereof. The parts are by weight.

Example A mixture of parts of acrylamide and 2 parts of allyl acetoacetate dissolved in 16 parts of methanol was placed in a glass container and the container sealed under an atmosphere of nitrogen. The reaction vessel was then exposed to ultraviolet light ior 20 hours, during which time the interpolymer was formed. The container was then opened and the acrylamide/allyl acetoacetate interpolymer was isolated by filtration and then dried.

Treatment 01 parts of a 10% aqueous solution of the interpolymer with 2 parts of a 2% aqueous solution of adipodihydrazide. which had been acidified with a small amount of acetic acid,

yielded a thermal reversible gel which had a melting point of 55 C. and a setting point of 42 C.

Interpolymers prepared in a similar manner from mixtures of acrylamide and allyl acetoacetate, in which the percentage of allyl acetoacetate was greater than on treatment with adipodihydrazide, gave gels which melted below room 1 temperature.

.6 Ca. (Ci. 2647-86-1) duction. For instance, other fi.-/-ethylenic aily unsaturated lower aliphatic alcohol esters of acetoacetic acid of the general formula:

0 t CHFC- ---NH: 7

where R is hydrogen, lower alkyl, preferably methyl or halogen, preferably chlorine, may be employed. Examples of amides of this type which can be employed for the preparation of the prod ucts of this invention include, in addition to acrylamide, methacrylamide, a-chloroacrylamide, a-fluoroacrylamide and a-bromacrylamide.

As indicated by the above example, the interpolymerization may advantageously be carried out in the presence of an inert solvent and in place of the methanol specified in the example other inert solvents may be employed. Examples of suitable solvents include lower aliphatic alcohols (i. e. ethanol, propanol, etc., in addition to methanol); also the lower aliphatic ethers, such as diethyl ether, diisopropyl ether, diisobutyl ether, di-n-butyl ether, dioxane; the aliphatic, cycloaliphatic and aromatic hydrocarbons, e. g. propane, the butanes, the pentanes, the hexanes, the heptanes, the octanes, etc. and mixtures thereof, cyclohexane, methyl-cyclohexane, benzene, toluene, xylene; dimethylformamide and pyridine.

I have found that the polymerization techniques commonly employed for the polymerization of acrylamide are efiective for the production of the novel interpolymers of this invention and the polymerization may readily be carried out either in a solution as above described or using ing, if desired, peroxide-type polymerization catv i u 3 alysts in place of the ultra-violet light specified in the example Thus, the novel interpolymers of the present invention have been produced by subiectin'g a mixture of parts of acrylamide and 2 parts of allyl acetoacetate in 10 parts of water to the action of ultra-violet light. It was found that the allyl acetoacetate was soluble due to the presence of acrylamide and a stiff gel was formed which, however, was not theme-reversible. This gel was then diluted to 5% aqueous solution while stirring with the addition of water and on treatment with adipodihydraside formed a thermo-reversible gel.

The novel interpolymers of this invention possess an acetoacetic acid group which substantially modifies the properties of the resin and renders them useful in a variety of applications. Thus, a

thepresenceoftheacetoaceticacldgroupin the realm produced in accordance with this invention enables them to act as a non-diifusible color coupling component for the formation of yellow asomethine dyes in certain types of color photography processes and useful resins have been obtained when the relative amount of the unsaturated alcohol acetoacetic acid ester employed in forming the interpolymers was varied from about 1% to about 40%. based on the weight of acrylamide. However. these novel in rpfllymers have been found to be particularly valuable for the production of thermo-reversible gels by treatment with a polrhydrazide as disclosed in my oopendlng application Serial No. 745,651, filed May 2, 1947, and when inter-polymers which are useful for this purpose are desired I prefer to use from about 5% to of the unsaturated alcohol acetoacetic acid ester, based on the-weight of the acrylamlde, or its equivalent, in their formation,

'since when less than 5% of the esters are employed an excessive amount of gelling agent (polyhydrazide) must be employed to form a thermoreversible gel while when more than 30% of the ester is employed in the polymerization process the resultant polymers form gels which melt below room temperature and thus would have relatively little utility in photography as a gelatin substitute.

1 claim: k

1. The interpolymers of an amide of an apethylenically unsaturated monocarboxylic acid of the formula:

wherein R is a member of the group consisting of hydrogen, halogen and methyl, with from 140% by weight thereof of a Bn-ethylenicaliy unsaturated lower aliphatic alcohol ester of acetoacetic acid said ester having the formula:

0 O CHrLCHsLO-OlipkCH wherein R1 is a member of the group consw ing of hydrogen, halogen and methol, and Re is amemberoithegroupcon'sistingofhrdrogen and methol. g l V 2. The interpolymer of acrylamide with from by weight thereof of allyl acetocetate;

8. The method of amide of an p-ethylenically unsaturated 'monocarbowlic acid of the formula:

0 OHFO-Er-NH:

wherein R is a member of the group consisting of hydrogen, halogen and methyl, with from 140% by weight thereof of a fia-etbylenicaliy unsaturated lower aliphatic alcohol ester of acetoacetic acidsaidesterhaving the formula:

O O V Y CELOELO-Qlig-(hyflli wherein Ri'is a member of the group consisting of hydrogen, halogen and methyl, and Reis a.

0 GR G-LN!!! wherein R is a member of the group consisting of hydrogen, halogen and lower alkyl radicals, with from 5-30% by welght'thereof of a p ethylenlcally unsaturated lower aliphatic alcohol ester of acetoacetic acid said ester having the formula: V

o o 7 cm -on.&-o cm-c=cn I r wherein R1 is a member of thegroup consisting of hydrogen, halogen and methyl, and R: is a member of the group consisting of hydrogen and methyl.

GIFEIN D.'JONES.

assurances crrsn The following references are of record in the ills of this patent:

UNITED STATES PATENTS- Number Home Date 2,164,188 7 Grell et al June 27, 1939 P lymerization 

